Born to strict parents, as a child she was an obedient girl that had a taste for reading. She idolized literature and wrote down a diary of Tanka and poetry. She had an admiration for Gallian literature and specialized in the Gallian language at the naval academy. She does not drink alcohol.
She was often picked on by others during the time of her training, including her instructors. Naoe also had the habit of, out of a vigorous fighting spirit, approaching the target until she reached the very limit. At times, this would result into a collision and the damaging of the Striker Unit, something that would earn her the nickname of "Destroyer" (デストロイヤー). On the other hand, because of this she would also come to specialize in tactics of closing in upon the opponent and then avoiding him by a paper-thin difference.
Simultaneously with her appointment as a Pilot Officer, Naoe was assigned to the European Dispatch Fleet and put in the Operation Barbarossa. Assigned to the ground units, she provided inland support for the Petersburg Invasion Operation. Afterwards, she took up the duty of defending Petersburg. Also, although it happened only on paper, she would later be moved from European Dispatch Fleet to the 201st Flying Corps and then to the 343rd Flying Corps.
In the middle of the fight in Europe, and with the intensification of the interchange of Witches between nations, she would later become a member of the 502nd Joint Fighter Wing when it was established.
Naoe can be described, in one word, as Napoleonic; despite her small size, she is bold and daring in the air, brash and sometimes belligerent socially. It's an attitude she forces on herself because of the war with the Neuroi: when her Witch abilities woke up, she roused herself by repeating the prayer: "to fight a Neuroi, one should have a ferocious personality". This attitude doesn't lend itself well to teamwork or cooperation, but under Flight Lieutenant Pokryshkin this is dampened somewhat, perhaps because she resembles an elder sister of Naoe's childhood, whom she remembers fondly.
Naoe embodies a daring combat-style, in which "if you run out of bullets use a blade, and if the blade breaks use a body blow". She also operates to good effect against big targets and her pet theory is that "the larger the enemy, the more worthwhile it is to defeat it". Her forte is to do a nose dive from just above the target and fire as the two pass by each other.
Her inherent magic is called Compression-formula Super Hardness Defensive Magic Circle (圧縮式超硬度防御魔方陣, asshuku-shiki choukoudo bougyo mahoujin), or simply Super Hard Shield (超硬シールド, choukou shiirudo). It is an ability that compresses the diameter of a magic shield until some dozens centimeters and raises its strength. There is this heroic saga of how, in the defensive battle of Petersburg, she defeated a Neuroi with the punch of a fist clad in this shield.
- Strike witches: Chii Sanya, cameo in chapter α-8
- Brave Witches: Dai 502 Butai Hasshin shimasu!
- World Witches: Contrail of Witches
- Brave Witches: 502nd Joint Fighter Wing
- Brave Witches Prequel: The Vast Land of Orussia
- Strike Witches: Kiseki no Rondo, in a group card
- Brave Witches VR: Operation Baba-Yaga - Counter attack in the snow
- She is also known by the pet name of "Nao" (ナオ).
- Her familiar is the bulldog.
- Naoe is based on Japanese flying ace Naoshi Kanno (菅野直). One of his nicknames was Bulldog, Naoe's familiar is a reference to this. Besides that, he was also nicknamed "Destroyer" and "Yellow Fighter".
- She has a scar on her left cheek, and cover it with patch.